Patent GB-528803-A (GB)
Title: Improvements in or relating to photographic sensitizing dyestuffs
IPC: C09B23/10
Filed: 1939-05-05
Abstract: 528,803. Sensitized photographic emulsions. COLLINS, R. B., and KENDALL, J. D. May 5, 1939, No. 13508. Samples furnished. [Class 98 (ii)] [Also in Group IV] Photographic sensitizing dyes are made by condensing a compound of the general formula where R 1  . . . R<SP>5</SP> represent hydrogen atoms or alkyl, ar alkyl or aryl groups, D is the residue of a 5-membered ring and n is O or a positive integer, with a quaternary salt of a heterocyclic nitrogen compound having as a reactive group a thioether or selenoether group (including an aryl-, alkyl- or aralkyl-thioether or selenoether group), or an aminovinyl type of group, i.e. a - (CH = CH)n-NH 2  group, where n is a positive integer, or an N-substituted group. of this type, in the α- or γ-position to the quaternary nitrogen atom, or with a quaternary salt of a 2-halogenated compound of the quinoline series, or with an aromatic aldehyde. The compounds of the above general formula are made by condensing a cyclic compound of the general formula such as a pyrazolone or rhodanic acid and its substitution products, with an aldehyde or ketone of the general formula such as acetaldehyde, propanaldehyde, crotonaldehyde, phenylacetaldehyde, acetone, acetophenone, ethylidene acetone and ethylidene acetophenone. Quaternary ammonium compounds which may be used for the condensation include those of thiazoles, thiazolines, oxazoles, oxozolines, selenazoles, selenazolines, pyridines, quinolines, indolenines, and quinazolines, including the corresponding polycyclic compounds such as benzthiazoles, naphthathiazoles and anthrathiazoles and also the diazoles described in Specification 425,609. In examples, (1) 1-methylthiolbenz-thiazole metho-p-toluene sulphonate is condensed with (a) 1-phenyl-3- methyl-4-isopropylidene-5-pyrazolone, (b) 1- phenyl - 4 - phenylmethylmethylene - 5 - pyrazolone, (c) 1-phenyl-4-isopropylidene-5-pyrazolone, (d) 1-phenyl-3-methyl-4-ethylidene-5- pyrazolone, (e) 1-phenyl-3-methyl-4-phenylmethylmethylene - 5 - pyrazolone, (f) 1 - p - chlorphenyl - 3 - methyl - 4 - isopropylidene - 5 - pyrazolone, (g) 1 - phenyl - 3 - methyl - 4 - # - phenylethylidene - 5 - pyrazolone, (h) 1 - phenyl - 3- methyl - 4 - methylcrotonylidene - 5 - pyrazolone, (i) ethylidene-rhodanic acid, (j) N- phenyl-ethylidene-rhodanic acid, (k) N-methylethylidene-rhodanic acid, (1) ethylidene thiohydantoin, and (m) crotonylidene-N-phenylrhodanic acid ; (2) 1-methylthiol benzthiazole etho-p-toluenesulphonate is condensed with 1 - phenyl - 3 - methyl - 4 - iso - propylidene - 5 - pyrazolone; (3) 1- methylthiol - benzoxazole metho-p-toluenesulphonate is condensed with 1 - phenyl - 3 - methyl - 4 - phenyl - methylmethylene - 5 - pyrazolone ; (4) 2 - # - acetanilidovinyl - 1 : 3 : 3 - trimethyl - indolenium iodide is condensed with 1-phenyl-3-methyl-4-phenylmethylmethylene-5-pyrazolone ; (5) 2-methylthiol-quinoline is condensed with 1-phenyl-4- phenylmethylmethylene-5-pyrazolone or with the 3-methyl compounds ; and (6) p-dimethylaminobenzaldehyde or 2-iodoquinoline ethiodide are condensed with 1-phenyl-3-methyl-4- isopropylidene-5-pyrazolone. Samples have been furnished under Sect. 2 (5) of the products obtained by condensing (1) 1-ethylquinoline-4-thione, methyl-p-toluene sulphonate and 1-phenyl-3-methyl-4-phenylmethylmethylene-5-pyrazolone and (2) 2-#- acetanilidobutadienyl - 3: 3 - dimethyl indolenine methiodide with 1-phenyl-3-methyl-4- phenylmethylmethylene-5-pyrazolone. Specification 513,596 also is referred to.